CN111094492B - Adhesive composition, adhesive comprising the same, and preparation method thereof - Google Patents
Adhesive composition, adhesive comprising the same, and preparation method thereof Download PDFInfo
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- CN111094492B CN111094492B CN201880054652.XA CN201880054652A CN111094492B CN 111094492 B CN111094492 B CN 111094492B CN 201880054652 A CN201880054652 A CN 201880054652A CN 111094492 B CN111094492 B CN 111094492B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/22—Heterocyclic compounds, e.g. ascorbic acid, tocopherol or pyrrolidones
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
- A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/04—Crosslinking with phenolic resin
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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Abstract
The present invention relates to an adhesive composition including polyvinyl alcohol and a water-soluble polyphenol compound, an adhesive including the same, and a method of preparing the same, and more particularly, to an adhesive composition which is less toxic, can be adhered even without a curing process unlike a conventional adhesive, can produce a gel by hydrogen bonding characteristics between a polyvinyl alcohol compound and a water-soluble polyphenol compound, and maintains adhesive properties in water.
Description
Technical Field
The invention relates to an adhesive composition, an adhesive containing the same and a preparation method thereof.
Background
Adhesives are materials used to attach one object to the surface of another object. According to the international organization for standardization (ISO) definition, "adhesion refers to a state in which two surfaces are bonded by chemical and/or physical force, and an adhesive is a material that allows bonding of two or more objects.
Adhesives are widely used in various fields including daily life and industrial work due to their convenience. These binders can be classified into inorganic binders and organic binders according to their main components. Organic binders can be further classified into synthetic organic binders and natural organic binders. In particular, synthetic organic adhesives may be further classified into resin-based adhesives including thermosetting resins or thermoplastic resins, rubber-based adhesives, and hybrid adhesives including phenol-formaldehyde adhesives and epoxy adhesives. However, in the case of synthetic organic binders, emission of harmful substances has recently become a serious problem. These problems are caused by the use of volatile organic solvents and the volatilization of unreacted monomers.
Thus, various adhesives have been developed, but there are often difficulties in developing compositions that can adhere in water. For common underwater adhesives, they are generally toxic. Therefore, there is a need to develop an adhesive composition that does not lose adhesive properties in water using harmless raw materials.
[ patent document ] Korean laid-open patent publication No.10-2012-0028175(2012.03.22), a binder composition comprising tannin, polyethylene glycol, and water, a lower alcohol, or a mixture thereof.
Disclosure of Invention
Technical problem
Accordingly, the inventors of the present invention have conducted many studies to develop an adhesive which is non-toxic, harmless to the human body, has moisture resistance, and does not require heating at the time of curing, and as a result, completed the present invention by confirming that an adhesive mixed with polyvinyl alcohol and a polyphenol compound is hardly soluble in water and can be adhered in an underwater environment or an environment not in water without a curing process.
Accordingly, it is an object of the present invention to provide an adhesive composition comprising a polyvinyl alcohol compound, a water-soluble polyphenol compound, and water.
It is another object of the present invention to provide an industrial adhesive, a medical adhesive, an adhesive for underwater use, a sealant for underwater use, an adhesive cake (adhesive pattern), a tape, a wound-healing wet dressing, a medical anti-adhesive, or a controlled drug delivery adhesive (controlled drug delivery adhesive) comprising the above composition.
Technical scheme
In order to achieve the above object, the present invention provides an adhesive composition comprising a polyvinyl alcohol compound, a water-soluble polyphenol compound, and water.
In this case, the polyvinyl alcohol compound may be in the form of a random copolymer.
At this time, the polyvinyl alcohol compound may be represented by the following formula 1.
[ formula 1]
Wherein n and m are a composition ratio of monomers of the polyvinyl alcohol compound, n is 0.7 or more and 1.0 or less, m is 0 or more and 0.3 or less, and n + m is 1.
At this time, the polyvinyl alcohol compound may include a functional group selected from the group consisting of a hydroxyl group (OH), an amine group (NH2), succinimidyl succinate, succinic acid, a thiol group (SH), an acrylate, an epoxy group, maleimide, nitrophenyl carbonate, pyridine disulfide, a tosylate group, an azide, a phosphate group, an oligoamine group ([ -CH2-CH2-NH- ] n), catechol, and catechol amine.
The water-soluble polyphenol compound may be at least one selected from the group consisting of a hydroxybenzoyl compound, a hydroxycinnamic acid compound, a flavonoid-based compound, a lignan-based compound, a distyryl compound, caffeic acid, chlorogenic acid, anthocyanidin, pyrogallol, ellagic acid, gallic acid, catechin, hydrolysable tannin, condensed tannin and theaflavin-3-gallate.
At this time, the hydrolyzable tannin may be at least one selected from the group consisting of tannic acid, gallotannin and ellagitannin.
At this time, the polyvinyl alcohol compound and the water-soluble polyphenol compound may be hydrogen-bonded to each other.
In this case, the tensile adhesive strength of the composition in water may be 10kPa or more.
At this time, the content of the polyvinyl alcohol compound may be 5 to 60% by weight based on the total weight of the composition.
At this time, the water-soluble polyphenol compound may be contained in an amount of 20 to 70% by weight, based on the total weight of the composition.
At this time, the content of water may be 10 to 60% by weight, based on the total weight of the composition.
At this time, the composition may further include at least one selected from the group consisting of an alcohol and an organic solvent.
At this time, the ratio of the tensile adhesive strength of the composition (tensile adhesive strength after 10 times of attachment and removal/initial tensile adhesive strength) may be 0.7 to 2.0, preferably 0.8 to 1.2, relative to the initial (one time) attachment and removal of the composition in water after 10 times of attachment and removal of the composition in water.
At this time, the ratio of the tensile adhesive strength in water of the composition to the tensile adhesive strength in water (tensile adhesive strength in water/tensile adhesive strength in water) is 0.7 to 1.3, preferably 0.8 to 1.2.
At this time, the composition can be used for industrial adhesives, medical adhesives, adhesives for underwater use, sealants for underwater use, adhesive cakes, tapes, wound-healing wet dressings, and medical anti-adherents.
In addition, the present invention provides a controlled drug release adhesive comprising the above composition.
At this time, the controlled drug release binder may be at least one selected from the group consisting of a sparingly-soluble drug, a therapeutic peptide, a protein, and an antibody.
In addition, the present invention provides a method for preparing an adhesive composition, the method comprising the steps of: (a) mixing a polyvinyl alcohol compound, a water-soluble polyphenol compound and water; and (b) obtaining the adhesive composition mixed and formed in step (a).
In addition, the present invention provides a method for preparing an adhesive composition, the method comprising the steps of: (a) dissolving a polyvinyl alcohol compound in water; (b) dissolving a water-soluble polyphenol compound in water; (c) mixing the respective dissolved substances obtained in step (a) and step (b) to form an adhesive composition; and (d) obtaining the adhesive composition formed in step (c).
At this time, any one of an alcohol and an organic solvent may be added to water.
Advantageous effects
The present invention relates to an adhesive composition comprising a polyvinyl alcohol compound and a water-soluble polyphenol compound, which is almost non-toxic and can be adhered even without a curing process unlike conventional adhesives, can prepare a gel by a hydrogen bonding property between the polyvinyl alcohol compound and the water-soluble polyphenol compound, and maintains an adhesive property in water.
The adhesive composition can be applied to various fields such as medical adhesives, adhesive pads, tapes, wound-healing moist dressings, drug-releasing adhesives or medical anti-adherents.
Drawings
Fig. 1 is a photograph showing a method of measuring adhesive force of the adhesive composition of the present invention.
Fig. 2 is a graph of the results obtained by measuring the tensile adhesive strength in water of the adhesive compositions prepared in examples 1 to 5.
Fig. 3 is a graph of the results obtained by measuring the tensile adhesive strength in water of the adhesive compositions prepared in examples 6 to 10.
Fig. 4 is a graph showing tensile adhesive strength measured while changing storage time after the adhesive composition prepared in example 8 was coated in water.
Detailed Description
In the present invention, an adhesive composition is proposed, which comprises a polyvinyl alcohol compound, a water-soluble polyphenol compound, and water, is almost non-toxic, can adhere even without a curing process unlike conventional adhesives, can produce a gel by hydrogen bonding characteristics between the polyvinyl alcohol compound and the water-soluble polyphenol compound, and maintains adhesive properties in water.
Hereinafter, the present invention will be described in more detail.
Adhesive composition
The adhesive composition referred to herein comprises a polyvinyl alcohol compound, a water-soluble polyphenol compound, and water. For typical underwater adhesives, it is generally toxic. However, the present invention provides an adhesive composition exhibiting water resistance in water using harmless raw materials.
The adhesive composition of the present invention includes polyvinyl alcohol. Polyvinyl alcohol compounds (poly (vinyl alcohol), PVA) were first synthesized by Herrmann and Haehnel in 1924 during the saponification of polyvinyl acetate (poly (vinyl acetate), PVAc) and began to be commercialized as a resin for vinylon fibers in japan after the second world war.
In general, polyvinyl alcohol (PVA) cannot be obtained by polymerization of vinyl alcohol because vinyl alcohol as a monomer is unstable, and is mainly prepared by generating PVAc from vinyl acetate by emulsion polymerization and then hydrolyzing it with alkali or acid.
The components of the PVA produced (n and m in the following formula 1) were determined based on the degree of hydrolysis of PVAc, which is generally referred to as the degree of saponification or the degree of hydrolysis. For example, if n is 0.88 and m is 0.12 in formula 1, the degree of hydrolysis of the PVA of formula 1 is 88%.
PVA prepared by saponification of PVAc is a white powdery polymer that is easy to form into films and fibers, and has high surface activity, high mechanical strength and adhesive strength, and excellent solubility and chemical reactivity. In addition, PVA is biodegradable, water-soluble, and degraded by bacteria found in soil, and thus has received attention as a sensitive material used in the protection of the environment. PVA has a very wide range of applications and is therefore widely used in applications ranging from household products to powerful industrial materials.
PVA is used in cardboard, plywood, office adhesives, adhesives for ferrite or ceramics, solid insect repellents, chamotte, fiber sizing agents, thickeners for color printing, washing powders, paper coatings or reinforcing agents, emulsifiers for emulsion polymerization or suspension polymerization, stabilizers, sponges, and the like, and has been widely used until recently in asbestos fibers, high-performance fibers for replacing concrete reinforcements, environmentally friendly water-soluble fibers, and various optical films and separators including polarizing films, according to molecular weight and stereoregularity, and also used as the most advanced materials such as hydrogels for replacing human organs, drug release systems, bioreactors, biosensors, and embolic materials for treating cancer and angioplasty.
The polyvinyl alcohol compound of the present invention may be in the form of a random copolymer, and specifically, a polyvinyl alcohol compound of formula 1 may be used.
[ formula 1]
Wherein n and m are a composition ratio of the polyvinyl alcohol compound, n is 0.7 or more and 1.0 or less, m is 0 or more and 0.3 or less, and n + m is 1.
In formula 1, when n is less than 0.7 or m is greater than 0.3, the content of PVA decreases, so that the water solubility (solubility) decreases, thereby making it difficult to prepare a solution of a polyvinyl alcohol compound.
In addition, the polyvinyl alcohol compound may include a functional group selected from the group consisting of a hydroxyl group (OH), an amine group (NH2), succinimidyl succinate, succinic acid, a thiol group (SH), an acrylate, an epoxy group, maleimide, nitrophenylcarbonate, pyridine disulfide (orthopyridyl disulfide), a tosylate group, an azide, a phosphate group, an oligoamine group ([ -CH2-CH2-NH- ] n), catechol, and catechol amine. For example, the epoxy functional group may be present in combination with each monomer of chemical formula 1, and it may react with a hydroxyl group (-OH) of the polyphenol compound to form a chemical bond.
The polyvinyl alcohol compound of the present invention can be used as polyvinyl alcohol compounds of various molecular weights depending on the field in which the adhesive composition is coated, and thus, is not specified in terms of the molecular weight of the polyvinyl alcohol compound, but preferably may have a weight average molecular weight (Mw) of 5,000 to 2,000,000. As the weight average molecular weight of the polyvinyl alcohol compound decreases, the flexibility of the prepared adhesive composition increases, and the adhesiveness (tack, stickiness) of the surface increases. As the weight average molecular weight of the polyvinyl alcohol compound increases, flexibility decreases and surface adhesiveness decreases, but it shows a characteristic that cohesion of the composition increases.
The content of the polyvinyl alcohol compound may be 5 to 60% by weight, more preferably 15 to 40% by weight, based on the total weight of the adhesive composition prepared in the present invention. If the content of the polyvinyl alcohol compound is less than 5% by weight, there is a problem in that the flexibility of the adhesive composition is reduced. If the content of the polyvinyl alcohol compound exceeds 60% by weight, there is a problem in that the water resistance is lowered and thus it is easily dissolved in water.
The adhesive composition of the present invention includes a water-soluble polyphenol compound.
As for the water-soluble polyphenol compound, a substance in which one of hydrogen atoms in a benzene ring (C6H6) is substituted with a hydroxyl group (-OH) is called phenol, and substances having two or more hydroxyl groups are collectively called water-soluble polyphenol, or polyphenol. Compounds having this structure are many in nature. Catechins contained in green tea, chlorogenic acid contained in coffee, and red or purple anthocyanin pigments contained in strawberry, eggplant, grape, black bean, and red bean are all polyphenol compounds. Additionally, polyphenolic compounds can be found in many varieties such as vegetables, fruits, cocoa, and red wine.
Polyphenols have antioxidant effect. Polyphenols have recently received attention because their functions are expected to contribute to health maintenance and disease prevention by acting as antioxidants in vivo. In addition, polyphenols prevent cholesterol from being absorbed into the digestive tract, thereby playing a role in reducing the cholesterol level in the blood.
The water-soluble polyphenol compound of the present invention may be at least one selected from the group consisting of a hydroxybenzoyl compound, a hydroxycinnamic acid-based compound, a flavonoid-based compound, a lignan-based compound, a distyryl compound, caffeic acid, chlorogenic acid, anthocyanidin, pyrogallol, ellagic acid, gallic acid, catechin, a hydrolyzable tannin, a condensed tannin and theaflavin-3-gallate, and specifically, the hydrolyzable tannin may be one or more selected from the group consisting of tannic acid, gallotannin and ellagitannin, but is not necessarily limited thereto.
In addition, the water-soluble polyphenol compound of the present invention may be specifically selected from the group consisting of tannic acid of formula 2, gallic acid of formula 3, ellagic acid of formula 4, catechin of formula 5, and polymers thereof. The weight average molecular weight of the water-soluble polyphenol compound is not particularly limited, but may be preferably 100 to 10,000.
[ formula 2]
[ formula 3]
[ formula 4]
[ formula 5]
The content of the water-soluble polyphenol compound may be 20 to 70% by weight, more preferably 30 to 55% by weight, based on the total weight of the adhesive composition prepared in the present invention. If the content of the water-soluble polyphenol compound is less than 20% by weight, there is a problem in the water-resistant adhesion of the adhesive composition. If the content of the water-soluble polyphenol compound exceeds 70% by weight, there is a problem that flexibility is reduced.
In the adhesive composition of the present invention, the polyvinyl alcohol compound and the water-soluble polyphenol compound may be hydrogen-bonded to each other, as shown in fig. 1 below.
[ FIG. 1]
Fig. 1 shows hydrogen bonds between tannic acid, which is a water-soluble polyphenol compound, and a polyvinyl alcohol compound. As shown in formula 6, the adhesive composition of the present invention may be prepared in the form of a gel due to the formation of hydrogen bonds between the polyvinyl alcohol compound and the water-soluble polyphenol compound. The adhesive composition of the present invention improves the solubility of PVA in water, thereby achieving the characteristics of an adhesive composition that can be used in an underwater environment.
Accordingly, the adhesive composition of the present invention may have excellent underwater adhesion, and in particular may have a tensile adhesive strength in water of 10kPa or more, preferably a tensile adhesive strength in water of 30kPa to 300kPa, more preferably a tensile adhesive strength of 50kPa to 100 kPa.
In particular, if the content ratio (on a solid basis) of the water-soluble polyphenol compound/polyvinyl alcohol compound is 0.5 or more, the tensile adhesive strength in water may be 30kPa to 300kPa, and more preferably, the tensile adhesive strength in water may be 50kPa to 100 kPa.
If the adhesive strength in water is less than 30kPa, the adhesive force is too low to be suitable for use as an underwater adhesive. If the adhesion is 300kPa or more, it may be difficult to achieve the composition claimed in the present invention. However, the upper limit of the adhesive force can be overcome depending on the pressure applied in the adhering step, the required time, the adhering time, the kind of water or solvent, and the temperature in the adhering step, and therefore, the upper limit of the tensile adhesive strength in water obtained by this is not necessarily limited.
In addition, it can be seen that since the ratio of the tensile adhesive strength in water to the tensile adhesive strength in water (tensile adhesive strength in water/tensile adhesive strength in water) of the adhesive composition of the present invention can be 0.7 to 1.3, preferably 0.8 to 1.2, the adhesive force in water is not lowered as compared with the adhesive force in water.
In addition, the composition may have a ratio of tensile adhesive strength after 10 times of attachment and removal in water with respect to initial (one time) attachment and removal (tensile adhesive strength after 10 times of attachment and removal/initial tensile adhesive strength) of 0.7 to 2.0, preferably 0.8 to 1.2, and may maintain adhesive force even when used for a long time in water.
The content of water contained in the adhesive composition of the present invention may be the remaining amount other than the polyvinyl alcohol compound and the water-soluble polyphenol compound, and is preferably 10 to 60 wt.%, based on the total weight of the composition.
The adhesive composition of the present invention may further comprise at least one selected from the group consisting of alcohols and organic solvents.
The alcohol used in the present invention is not particularly limited, but may be a lower alcohol such as methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, n-pentanol, isopentanol, n-hexanol, preferably ethanol.
The organic solvent used in the present invention is not particularly limited.
In addition, the adhesive composition of the present invention may contain an additive for improving cohesion to improve interfacial failure or cohesive failure characteristics resulting in the destruction of the adhesive itself. The additive may be an additive capable of hydrogen bonding, chelate bonding, covalent bonding through hydrophobic interaction, and ionic bonding with a polyvinyl alcohol compound or a water-soluble polyphenol compound, and specifically, at least one selected from the group consisting of inorganic particles, metal particles, DNA, metal oxides or metal ions, BSA, and proteins may be used.
In addition, the adhesive composition of the present invention may further include an additive for improving physical properties thereof, etc., and may further include a thickener for improving viscosity, a plasticizer for reducing viscosity, a dye and a pigment for coloring, an ultraviolet absorber and an ultraviolet stabilizer for light stability, an antistatic agent for preventing static electricity.
The adhesive composition of the present invention can be used in industrial adhesives, medical adhesives, adhesives for underwater use, sealants for underwater use, adhesive cakes, tapes, wound-healing moist dressings and medical anti-adherents.
In addition, the adhesive composition of the present invention can be used for bonding of adherends made of wood or wooden materials.
As used herein, the term "bond" refers to the conventional meaning that cures at an initial time and then becomes inelastic over time, and also refers to being difficult to reattach when removed again. However, as used herein, the term "adhesive" is intended to include "tack". The term "tack" refers to a condition that can be easily adhered by pressure and can be re-adhered several times after removal, in the form of a state that retains viscoelastic properties. The adhesive composition of the present invention has properties as an adhesive.
The adhesives of the invention are non-toxic. Therefore, the adhesive composition of the present invention can be used as a medical adhesive and can be directly contacted with the skin, and is characterized in that it has no toxicity and danger even when the adhesive is used in the body and flows into body fluid and blood and thus directly intervenes in the living body.
Thus, the adhesive composition of the present invention can be used in medical adhesives, wet wound healing dressings, anti-tack agents, and the like.
The medical adhesive means an adhesive that can be applied to a wide range of fields of packaging of medical instruments in a broad sense to surgical adhesion, and hemostasis, and has biocompatibility, and thus can be directly used on the skin, and generally has no toxicity and risk at all even when directly introduced into a living body, and thus can be used in the body. For use as a medical adhesive, the medical adhesive should have biodegradability, water resistance, sterility, non-toxicity, and hemostatic effects, in addition to biocompatibility, and should not interfere with the healing of a living body. The adhesive of the present invention has utility as a medical adhesive, including use as an adhesive. More specifically, the adhesives of the invention can be used in vivo as surgical adhesion hemostats and as medical adhesives for post-colonic incision sutures.
An anti-adhesion agent refers to a material that acts as a physical barrier at the site where adhesion is desired for a period of time and thus serves to prevent the formation of an adhesion between adjacent tissues. Therefore, the anti-adhesive agent should be decomposed or absorbed into the body after a certain period of time, and thus should not remain as a foreign substance. The adhesive composition of the present invention may be included in the preparation of an anti-tack agent for preventing adhesion that may be caused after surgery.
The wound-healing moist dressing has sufficient antibacterial activity to effectively treat or prevent severe infections caused by various pathogenic bacteria causing wound site deterioration, delayed treatment and complications, and also provides a moist environment through absorption of exudate, thereby rapidly increasing the growth rate of epithelial cells for skin regeneration and relieving pain, shortening the treatment time, minimizing scars after treatment, and the like. Therefore, when used in a wound healing moist dressing, it must be non-toxic. Since the adhesive composition of the present invention is non-toxic, it can be used as a wound healing moist dressing.
The adhesive of the present invention is characterized by having water resistance that can be used even in an aqueous environment. As used herein, the term "water resistance" refers to a property capable of maintaining adhesion even in an environment in which water is present, for example, in an environment in which moisture is present. In order to have water resistance, it must not be well dissolved in a substance having high humidity or an aqueous solution containing water, and must be able to stably maintain adhesion even in the presence of fluid flow. Since the adhesive of the present invention has a property of being slightly soluble in water, the adhesive of the present invention can be used as an adhesive for underwater use having moisture resistance, a sealant for underwater use, or the like.
In addition, the adhesive composition of the present invention can be used as a controlled drug release adhesive, and thus, a therapeutic drug may be contained for this purpose, and for example, a sparingly-soluble drug, a therapeutic peptide, a protein, and an antibody, which can be released by the controlled drug release adhesive, may be contained. Without being limited to these, examples of sparingly soluble substances include paclitaxel and doxorubicin and the like having low molecular weights, examples of therapeutic peptides include somatostatin, calcitonin, vasopressin, platelet coagulation inhibitory peptide (platelet aggregation inhibitor), gonadotropin releasing hormone and the like, and examples of proteins and antibodies include interleukin family, Erythropoietin (EPO), granulocyte colony stimulating factor (G-CSF), human growth hormone and the like. In the present invention, the type of the drug is not particularly limited.
In addition, the present invention relates to a method for preparing an adhesive composition, comprising the steps of: (a) mixing a polyvinyl alcohol compound, a water-soluble polyphenol compound and water; and (b) obtaining the adhesive composition mixed and formed in step (a). For each step, the preparation method of the adhesive composition of the present invention is described below
The step (a) is a step of mixing a polyvinyl alcohol compound, a water-soluble polyphenol compound and water.
The adhesive composition of the present invention is prepared by mixing a polyvinyl alcohol compound, a water-soluble polyphenol compound, and water. In addition to water, a solvent of any one of alcohol and organic solvent may be further added. In mixing the substances, the order of mixing is not limited to the order described above.
Step (b) is a step of obtaining the binder composition mixed and formed in step (a).
The mixture of step (a) does not cause additional reaction during mixing, and an adhesive composition can be obtained without a separate process. When the two mixtures are mixed, the gelation process rapidly proceeds, and a liquid composed of water, alcohol, an organic solvent, an unreacted polyvinyl alcohol compound and an unreacted polyphenol compound and a binding substance in a gel state are separated.
In addition, the present invention relates to a method for preparing an adhesive composition, comprising the steps of: (a) a step of dissolving a polyvinyl alcohol compound in water; (b) a step of dissolving a water-soluble polyphenol compound in water; (c) a step of mixing each dissolved substance obtained in the step (a) and the step (b) to form an adhesive composition; and (d) a step of obtaining the adhesive composition formed in step (c). The preparation method of each step is as follows.
The step (a) is a step of dissolving the polyvinyl alcohol compound in water, and the step (b) is a step of dissolving the water-soluble polyphenol compound in water. In step (a) and step (b), any one of an alcohol and an organic solvent may be further added in addition to water. These are processes in which the water-soluble polyphenol compound and polyvinyl alcohol compound which are the components of the present invention described above are dissolved in water, respectively, to make them easy to mix, and these processes are separate steps. In addition, a buffer for adjusting pH may be used in preparing the dissolved substance.
Step (c) is a step of mixing the respective dissolved substances obtained in step (a) and step (b) to form an adhesive composition.
This step is a step of forming the adhesive composition by mixing the polyvinyl alcohol compound of the present invention and the dissolved matter of the water-soluble polyphenol compound, and the mixing order is not limited to the order, and the mixing volume ratio is the same as described above.
Step (d) is a step of obtaining the adhesive composition of step (c).
The mixture of the present invention does not cause additional reaction during the mixing process, the binder composition can be obtained from the mixture without a separate process, and the brown material corresponds to the binder composition of the present invention.
Hereinafter, the preparation method of the adhesive composition of the present invention will be described in more detail by examples of the present invention. It should be understood that the present invention is not limited to these examples.
Examples
Preparation of adhesive composition
[ examples 1 to 5]
20 g of a polyvinyl alcohol compound of formula a (PVA, weight average molecular weight 13000-23000, degree of hydrolysis 87-89%) was added to 80 g of water and stirred in an oven at 85 ℃ for 5 hours to prepare a 20 wt.% aqueous PVA solution. A 40 wt.% aqueous PVA solution was prepared in the same manner as described above.
50 grams of tannic acid (formula b) was added to 50 grams of water and stirred at room temperature for 24 hours to make a 50 wt.% aqueous TA solution. Aqueous solutions of TA were prepared in the same manner as above at 10, 20, 30 and 40 wt.%, respectively.
The aqueous solution of polyvinyl alcohol and the aqueous solution of tannic acid were quantified in the same amounts (weight ratio of 1:1) as shown in tables 1 and 2, and stirred for 10 minutes using a spatula to prepare adhesive compositions.
Table 1:
table 2:
thereafter, they were treated at 10kRPM for 10 minutes using a centrifuge to obtain a bottom-sinking adhesive composition.
[ formula a ]
[ formula b ]
Comparative example 1
An adhesive composition was prepared by mixing 38. mu.l of linear polyethylene glycol (PEG, weight average molecular weight of 2kDa) having a concentration of 1g/mL with 162. mu.l of tannic acid (formula b) having a concentration of 1g/mL according to the method described in example 1 of Korean patent No. 10-1307367.
Examples of the experiments
Experimental example 1: measurement of adhesion in water
In order to measure the adhesive force in water of the adhesive compositions prepared in examples 1 to 10 and comparative example 1, a device was designed as shown in fig. 1 to measure the tensile adhesive strength in water.
A cylindrical sample having a diameter of 10mm was made of SUS, attached to a water bath, and filled with water, and then 40mg of the adhesive composition was coated on the cylindrical sample in water. The adhesive composition was pressed with a force of 5N for 30 seconds using a cylindrical sample made of SUS material having a diameter of 10mm, and then removed at a speed of 1mm/min to measure its tensile adhesive strength in water, and its procedure was as shown in fig. 1.
In addition, the tensile adhesive strength in water of the adhesive compositions prepared in examples 1 to 10 is shown in fig. 2 and 3. As a result of analyzing the tensile adhesive strength in water of examples 1 to 10, it was confirmed that the tensile adhesive strength in water was expressed as 30kPa or more in the case where the TA/PVA content ratio (TA solid/PVA solid) for preparing the adhesive composition was 0.5 or more, and that the adhesive force showed the maximum value when the TA/PVA content ratio (TA solid/PVA solid) was 1.0 or more. It was confirmed that the adhesive composition thus prepared exhibited higher adhesive properties as compared to comparative example 1. Therefore, in the preparation of the binder composition, the binder composition produced at a TA/PVA content ratio (TA solid/PVA solid) of 0.5 or more employed in the initial mixing is preferable as the binder, and more preferably, the TA/PVA content ratio (TA solid/PVA solid) is determined to be 1.0 or more. The binder composition produced at a TA/PVA content ratio (TA solid/PVA solid) of 0.5 or more and 4.0 or less employed in the initial mixing is preferably used as the binder, and more preferably, the TA/PVA content ratio (TA solid/PVA solid) is determined to be 2.0 or more.
In the case of two materials mixed at a TA/PVA content ratio of 2.0 or 4.0 or more employed in the initial mixing, TA does not participate in the composition formed by hydrogen bonds or interactions at all, but is present as a supernatant. Due to this phenomenon, there is a disadvantage that the yield of the resulting composition is reduced. Of course, since the TA solution can be reused by a method of reprocessing the solution present as the supernatant, the TA/PVA content ratio (TA solid/PVA solid) employed in the initial mixing in the present invention is not necessarily the upper limit.
Experimental example 2: measurement of adhesion in stored Water
The degree of change of the adhesive force with time was confirmed after coating in water and storing for a certain time. The adhesive composition prepared in example 8 was measured for tensile adhesive strength in the same manner as in experimental example 1 while changing the storage time after coating in water.
As shown in fig. 4, it was found that the ratio of the initial tensile adhesive strength in water within 1 hour to the tensile adhesive strength in water after 24 hours (initial tensile adhesive strength in water within 1 hour/tensile adhesive strength in water after 24 hours) after coating in water was 0.8 to 1.2, and thus the magnitude of the change in adhesive force with time was very small.
Experimental example 3: measurement of adhesion force according to attachment and removal in water
For the adhesive composition prepared in example 3, the tensile adhesive strength according to the number of times of attachment and removal in water was measured, and the results are shown in table 3.
As shown in table 3, it was confirmed that the adhesive force was not reduced even if the adhesion and removal were performed ten times in water, and it was confirmed that the width of the change in the ratio of the tensile adhesive strength after the initial (one time) and the ten times of adhesion and removal was 0.8 to 1.2 or less.
Thus, it was confirmed that the adhesive composition of the present invention can be attached and removed in water many times.
Table 3:
experimental example 4: measurement of tensile bond Strength in and out of Water
The tensile adhesive strength in water and not in water was measured using the adhesive composition prepared in example 3, and the measurement was performed while changing the applied pressure thereof to 5N and 10N. The results are shown in Table 4.
TABLE 4
As shown in table 4, the adhesive composition of the present invention exhibited excellent tensile adhesive strength in water and not in water, and it was confirmed that the ratio of the tensile adhesive strength in not water and in water was maintained at a constant ratio (0.8 to 1.2).
Claims (21)
1. An adhesive composition comprising a polyvinyl alcohol compound, a water-soluble polyphenol compound and water,
wherein the polyvinyl alcohol compound is present in an amount of 15 to 40 wt.%, based on the total weight of the composition,
wherein the content ratio of the water-soluble polyphenol compound/the polyvinyl alcohol compound is 0.5 or more on a solid basis,
wherein the weight average molecular weight of the polyvinyl alcohol compound is 13000 to 23000.
2. The adhesive composition of claim 1, wherein the polyvinyl alcohol compound is in the form of a random copolymer.
3. The adhesive composition according to claim 1, wherein the polyvinyl alcohol compound is represented by the following formula 1,
[ formula 1]
Wherein n and m are a composition ratio of monomers of the polyvinyl alcohol compound, n is 0.7 or more and 1.0 or less, m is 0 or more and 0.3 or less, and n + m is 1.
4. The adhesive composition of claim 1, wherein the polyvinyl alcohol compound comprises a functional group selected from the group consisting of hydroxyl (OH), amine group NH2, succinimidyl succinate, succinic acid, thiol group (SH), acrylate, epoxy, maleimide, nitrophenylcarbonate, pyridine disulfide, tosylate, azide, phosphate, oligomeric amine group [ -CH2-CH2-NH- ] n, catechol, and catechol amine.
5. The binder composition according to claim 1, wherein the water-soluble polyphenol compound is at least one selected from the group consisting of a hydroxybenzoyl compound, a hydroxycinnamic acid compound, a flavonoid-based compound, a distyryl compound, caffeic acid, chlorogenic acid, anthocyanidin, pyrogallol, gallic acid, ellagic acid, catechin, a hydrolyzable tannin, a condensed tannin, and theaflavin-3-gallate.
6. The binder composition of claim 5, wherein the hydrolysable tannin is at least one selected from the group consisting of tannic acid, gallotannins, and ellagitannins.
7. The adhesive composition according to claim 1, wherein the polyvinyl alcohol compound and the water-soluble polyphenol compound are hydrogen-bonded to each other.
8. The adhesive composition according to claim 1, wherein the composition has a tensile adhesive strength in water of 30kPa or more.
9. The adhesive composition of claim 1, wherein the water-soluble polyphenol compound is present in an amount of 20 wt.% to 70 wt.%, based on the total weight of the composition.
10. The adhesive composition of claim 1, wherein the water is present in an amount of 10 to 60 wt.%, based on the total weight of the composition.
11. The adhesive composition according to claim 1, wherein the composition further comprises at least one selected from the group consisting of an alcohol and an organic solvent.
12. The adhesive composition according to claim 1, wherein the ratio of tensile adhesive strength in water to tensile adhesive strength not in water of the composition, i.e., tensile adhesive strength in water/tensile adhesive strength not in water, is 0.8 to 1.2.
13. The adhesive composition according to claim 1, wherein the ratio of the tensile adhesive strength after 10 times of attachment and removal in water with respect to the initial attachment and removal, i.e., one time of attachment and removal, i.e., the tensile adhesive strength after 10 times of attachment and removal/initial tensile adhesive strength is 0.8 to 1.2.
14. The adhesive composition according to claim 1, wherein the composition has a ratio of initial tensile adhesive strength in water within 1 hour to tensile adhesive strength in water after 24 hours, i.e., initial tensile adhesive strength in water within 1 hour/tensile adhesive strength in water after 24 hours, of 0.8 to 1.2 after coating in water.
15. The adhesive composition of claim 1, wherein the composition is used in industrial adhesives, medical adhesives, adhesives for underwater use, sealants for underwater use, adhesive cakes, tapes, wound-healing moist dressings, medical anti-adherents.
16. The adhesive composition according to claim 1, wherein the composition is used for adhesion of adherends made of wood or wooden materials.
17. A controlled drug release adhesive comprising the composition of claim 1.
18. The controlled drug release adhesive of claim 17, wherein the controlled drug release adhesive comprises any one or more selected from the group consisting of a sparingly soluble drug, a therapeutic peptide, a protein, and an antibody.
19. A method of preparing an adhesive composition comprising the steps of:
(a) mixing a polyvinyl alcohol compound, a water-soluble polyphenol compound and water; and (b) obtaining the adhesive composition mixed and formed in step (a).
20. A method of preparing an adhesive composition comprising the steps of:
(a) dissolving a polyvinyl alcohol compound in water;
(b) dissolving a water-soluble polyphenol compound in water;
(c) mixing the respective dissolved substances obtained in step (a) and step (b) to form an adhesive composition; and
(d) obtaining the adhesive composition formed in step (c).
21. The method of preparing an adhesive composition according to claim 19 or 20, wherein one or more solvents of an alcohol and an organic solvent are further added to the water.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0106364 | 2017-08-23 | ||
| KR20170106364 | 2017-08-23 | ||
| KR10-2018-0097589 | 2018-08-21 | ||
| KR1020180097589A KR102368895B1 (en) | 2017-08-23 | 2018-08-21 | An adheisve composition, the adhesive having the same, the manufacturing method thereof |
| PCT/KR2018/009654 WO2019039858A1 (en) | 2017-08-23 | 2018-08-22 | Adhesive composition, adhesive comprising same, and manufacturing method therefor |
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| CN111094492A CN111094492A (en) | 2020-05-01 |
| CN111094492B true CN111094492B (en) | 2022-02-08 |
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| EP (1) | EP3674379A4 (en) |
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| EP4024532B1 (en) | 2019-12-03 | 2024-05-29 | Contemporary Amperex Technology Co., Limited | Secondary battery, method for preparing the same, copolymer and apparatus |
| KR102609171B1 (en) * | 2021-01-13 | 2023-12-01 | 삼성에스디아이 주식회사 | Adhesive composition for polarizing plate, polarizing plate and optical display apparatus |
| CN112870989B (en) * | 2021-01-11 | 2023-03-17 | 中化(宁波)润沃膜科技有限公司 | Anti-pollution composite reverse osmosis membrane and preparation method thereof |
| WO2022202138A1 (en) * | 2021-03-23 | 2022-09-29 | 三菱ケミカル株式会社 | Composition for sustained-release solid preparation, sustained-release tablet using same and manufacture method thereof |
| KR102572019B1 (en) | 2021-06-08 | 2023-08-31 | 왕미정 | Waterproof structure for rooftop and waterproofing methods for rooftop |
| CN114149777B (en) * | 2021-12-21 | 2023-04-11 | 忻州师范学院 | Phenol-based multifunctional solvent-free adhesive and preparation method thereof |
| CN114250053B (en) * | 2021-12-30 | 2022-09-20 | 山东大学 | Preparation and use method of polyphenol-polyethylene glycol-based eutectic adhesive |
| CN114806464A (en) * | 2022-05-24 | 2022-07-29 | 宁波锋成先进能源材料研究院有限公司 | Environment-friendly nontoxic adhesive and preparation method thereof |
| BR102022012591A2 (en) * | 2022-06-23 | 2024-01-02 | Inst Hercilio Randon | Composition for adhesion of metals and composite materials, process for their preparation, friction composite, friction composite forming process |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB488033A (en) | 1935-12-30 | 1938-06-29 | Carborundum Co | Improvements in abrasive products and methods of manufacturing them |
| US4564649A (en) * | 1984-04-16 | 1986-01-14 | H. B. Fuller Company | Polyvinyl alcohol and lignin sulfonate containing adhesive |
| JPS6162573A (en) * | 1984-09-03 | 1986-03-31 | Isao Sakata | Tannin adhesive composition |
| CA1289297C (en) | 1987-12-08 | 1991-09-17 | Toshihide Shimizu | Method of preventing polymer-scale formation |
| JP2845630B2 (en) | 1991-02-22 | 1999-01-13 | 信越化学工業株式会社 | Method for preventing scale adhesion during polymer production |
| WO1997030114A1 (en) | 1996-02-20 | 1997-08-21 | Kbms Industrial Holdings, Ltd. | Modified polyvinyl alcohol adhesive for binding aggregate particles |
| US6146497A (en) | 1998-01-16 | 2000-11-14 | Hercules Incorporated | Adhesives and resins, and processes for their production |
| JP4479867B2 (en) * | 2000-04-21 | 2010-06-09 | 田島ルーフィング株式会社 | Roofing adhesive cloth, roofing laminated with it, and waterproof construction method using the same |
| WO2005056708A2 (en) | 2003-12-09 | 2005-06-23 | Spherics, Inc. | Bioadhesive polymers with catechol functionality |
| KR100733926B1 (en) | 2005-04-22 | 2007-07-02 | 주식회사 엘지화학 | Functional adhesive, Construction material using the same, and method for preparing the adhesive |
| US20130045393A1 (en) | 2007-07-12 | 2013-02-21 | Dsm Ip Assets B.V. | Organic nano-particles and process for their preparation |
| CN101475790B (en) * | 2008-01-04 | 2012-10-10 | 杨光 | Novel timber adhesive and preparation thereof |
| KR101103423B1 (en) | 2009-09-04 | 2012-01-06 | 아주대학교산학협력단 | In situ forming hydrogel for tissue adhesives and biomedical use thereof |
| KR101307367B1 (en) | 2010-09-14 | 2013-09-25 | 주식회사 이노테라피 | Adhesive composition comprising tannin, polyethylene glycol, and water, low carbon alcohol or the mixture thereof |
| US10160891B2 (en) | 2012-02-08 | 2018-12-25 | Honeywell International Inc. | High performance water-based tackified acrylic pressure sensitive adhesives |
| WO2015115453A1 (en) | 2014-01-30 | 2015-08-06 | テイカ製薬株式会社 | Composition for orally rapidly disintegrating solid preparation |
| MX2016013504A (en) * | 2014-04-15 | 2017-01-16 | Honeywell Int Inc | High performance water-based adhesion compositions and applications. |
| GB201412706D0 (en) | 2014-07-17 | 2014-09-03 | Knauf Insulation And Knauf Insulation Ltd | Improved binder compositions and uses thereof |
| CR20170379A (en) | 2015-02-16 | 2018-01-25 | Petro Andriyovych Manoryk | HEMOSTATIC COMPOSITION AND HEMOSTATIC DEVICE (VARIANTS) |
| CN105950071A (en) | 2016-06-17 | 2016-09-21 | 枞阳县新天地高新材料有限公司 | High-performance glue |
| CN106364202B (en) | 2016-08-28 | 2019-02-05 | 杭州华大海天科技有限公司 | Temperature-sensitive viscous instant-drying type thermal sublimation transfer printing digital cloth |
| CN106668931A (en) | 2017-01-05 | 2017-05-17 | 温州医科大学附属第二医院、温州医科大学附属育英儿童医院 | Biological adhesive and preparation method thereof |
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| US20200362208A1 (en) | 2020-11-19 |
| TWI771475B (en) | 2022-07-21 |
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| US11613679B2 (en) | 2023-03-28 |
| JP7032517B2 (en) | 2022-03-08 |
| JP2020531649A (en) | 2020-11-05 |
| TW201912750A (en) | 2019-04-01 |
| CN111094492A (en) | 2020-05-01 |
| EP3674379A1 (en) | 2020-07-01 |
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